JP7210462B2 - Oil-in-water emulsified cosmetic using ultrafine emulsion - Google Patents

Description

Related application

The present invention is based on the priority claim of Japanese Patent Application: Japanese Patent Application No. 2017-191833 (filed on September 29, 2017), and the entire description of the application is incorporated herein by reference. shall be

TECHNICAL FIELD The present invention relates to an oil-in-water emulsified cosmetic using an ultrafine emulsion, and more particularly to improvement of transparency and increase in viscosity of the cosmetic.

Hydrophobically modified Ethoxylated URethane Copolymer (HEUR) is also blended in cosmetic compositions etc. as a water-soluble thickener with excellent viscosity stability and usability (see, for example, Patent Document 1). . A composition thickened with a hydrophobically modified polyether urethane gives a peculiar plump feel and is attractive as a cosmetic base to be applied to the skin or the like.
However, although the composition has the feature that it is difficult for the viscosity to change due to changes in the salt concentration and pH of the composition to be co-blended, there is a problem that the viscosity decreases when stored at a high temperature (for example, 50 ° C.). rice field. Patent Document 1 suggests that the addition of a water-soluble polymer such as carboxyvinyl polymer or xanthan gum in addition to hydrophobically modified polyether urethane can suppress the decrease in viscosity at high temperatures.

Patent Documents 2 and 3 describe that a synergistic thickening effect is obtained by combining a hydrophobically modified polyether urethane and a microgel thickening agent. In Patent Document 2, a microgel obtained by pulverizing a gel composed of a hydrophilic compound having gelling ability such as agar and gellan gum is blended. -acrylamido-2-methylpropanesulfonic acid) is dissolved in the dispersed phase and microgel obtained by radical polymerization in the dispersed phase is blended.

However, when the water-soluble polymer described in Patent Document 1 and the thickener microgel described in Patent Documents 2 and 3 are co-blended with a composition containing a hydrophobically modified polyether urethane, high-temperature stability is improved and synergy is obtained. However, due to the mixing of a third component such as an oily component or an amphipathic substance, the unique springy feel of the composition thickened with the hydrophobically modified polyether urethane is lost. There was something that was broken.

Under these circumstances, in Patent Document 4, an elastic gel composition was developed in which the high-temperature stability of an oil-in-water emulsion composition thickened with a hydrophobically-modified polyether urethane was improved, and a unique plump feel was maintained. was done.

However, the elastic gel composition obtained in Patent Document 4 did not have sufficient viscosity. In addition, even if a thickening agent that is generally used in cosmetics is used, the appearance often becomes cloudy, and there is a problem that the viscosity decreases.

Japanese Patent No. 3828700 Japanese Patent No. 4979095 Japanese Patent No. 5035948 JP-A-2016-88868

Therefore, the present invention has been made in view of the above-mentioned prior art, and the problem to be solved is that even in the case of a high-pressure emulsified cosmetic, it is possible to obtain a high-viscosity oil-in-water while maintaining a good appearance with a sense of transparency. To provide a type emulsified cosmetic.

As a result of intensive research by the present inventors to solve the above-mentioned problems, by blending an ultrafine emulsion, stearoxy hydroxypropylmethyl cellulose and a nonionic surfactant, it is possible to maintain a good appearance with a sense of transparency. The inventors have found that an oil-in-water emulsified cosmetic having a high viscosity can be obtained while maintaining the composition.

一般式(1)中、Ｒ1、Ｒ2、及びＲ3は、同一又は異なって、－［ＣＨ2ＣＨ（ＣＨ3）Ｏ］x－Ｒ4、－［ＣＨ2ＣＨ2Ｏ］y－Ｒ4、及び－［ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ］z－Ｒ4から選ばれる１種以上の基を示す。ここで、ｘ、ｙ、及びｚは、同一又は異なって、０～４の整数を示す。
また、Ｒ4は、水素原子、炭素数が１～４の直鎖状又は分岐状のアルキル基、及び炭素数が１０～２８の直鎖状のアルキル基から選ばれる１種以上の基を示し、且つ一般式(1)中で少なくとも１カ所のＲ4は炭素数が１０～２８の直鎖状のアルキル基である。炭素数が１０～２８の直鎖状のアルキル基としては、好ましくは炭素数１２～２２の直鎖状のアルキル基が挙げられる。
また、一般式(1)中、ｎは２００～２０００００の整数を示す。

前記水中油型乳化化粧料において、粘度が、２０００～１０００００mPa・sであることが好適である。
前記水中油型乳化化粧料において、（Ａ）超微細エマルションの平均粒径５nm～３００nmの油滴であることが好適である。That is, the oil-in-water emulsified cosmetic according to the present invention is
(A) 10 to 50% by mass of an ultrafine emulsion containing (a1) and (a2) below;
(a1) an anionic surfactant (a2) a linear higher alcohol having 16 or more carbon atoms capable of forming an α-gel in water together with (a1) (B) stearoxyhydroxypropyl methylcellulose represented by the following general formula (1) 0.2 to 2% by mass;
(C) 0.1 to 1% by mass of a nonionic surfactant;
It is characterized by blending

In general formula (1), R1, R2, and R3 are the same or different, --[CH2CH(CH3)O]x-R4, --[CH2CH2O]y-R4, and --[CH2CH(OH)CH2O]z - represents one or more groups selected from R4; Here, x, y and z are the same or different and represent integers from 0 to 4.
R4 represents one or more groups selected from a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear alkyl group having 10 to 28 carbon atoms, At least one R4 in the general formula (1) is a linear alkyl group having 10 to 28 carbon atoms. The linear alkyl group having 10 to 28 carbon atoms preferably includes a linear alkyl group having 12 to 22 carbon atoms.
In general formula (1), n represents an integer of 200-200,000.

The oil-in-water emulsified cosmetic preferably has a viscosity of 2,000 to 100,000 mPa·s.
In the oil-in-water emulsified cosmetic, (A) the ultrafine emulsion preferably has oil droplets having an average particle size of 5 nm to 300 nm.

According to the present invention, by blending an ultrafine emulsion, a specific stearoxyhydroxypropylmethylcellulose, and a nonionic surfactant, it is possible to obtain an oil-in-water emulsified cosmetic having a high viscosity while maintaining good appearance. I found out.

The oil-in-water emulsified cosmetic according to the present invention is obtained by blending (A) an ultrafine emulsion, (B) stearoxyhydroxypropyl methylcellulose, and (C) a nonionic surfactant. .

(A) the ultrafine emulsion used in the present invention contains (a1) an anionic surfactant and (a2) a linear higher alcohol having 16 or more carbon atoms capable of forming an α-gel in water together with (a1). Characterized by The α-gel is generally an aggregate formed in water by a higher aliphatic alcohol and a hydrophilic surfactant, and has an α-structure (Shoji Fukushima, "Physical Chemistry of Cetyl Alcohol", Fragrance Journal). means The gel preferably has a gel transition temperature of 60° C. or higher from the viewpoint of stability.

(A) Ultrafine Emulsion Emulsion refers to an emulsion that has been conventionally used for cosmetics and the like.
The ultrafine emulsion used in the present invention is characterized by oil droplets having an average particle size of 5 nm to 300 nm. Preferably, it is an oil droplet of 10 nm to 150 nm. If it is larger than 300 nm, the appearance of the composition may change, failing to obtain the desired transparent appearance of the present invention.

The (A) ultrafine emulsion used in the present invention can be prepared by a method such as an aggregation method or a dispersion method.
The coagulation method is a colloidal preparation method that utilizes surface chemical properties, and is a method in which a uniformly dissolved state is brought into a supersaturated state by some means to emerge as a dispersed phase. As specific methods, the HLB temperature emulsification method, the phase inversion emulsification method, the non-aqueous emulsification method, the D phase emulsification method, the liquid crystal emulsification method, and the like are known.
The dispersion method is a method of refining aggregates of the dispersed phase by force. Specifically, it is a method of emulsifying using the crushing force of an emulsifier.

A dispersing method by high-pressure emulsification as described in Japanese Patent No. 3398171 is preferably used in the present invention. High-pressure emulsification is a method of pre-emulsifying an aqueous phase component and an oil phase component, if necessary, using a homomixer or the like, and obtaining an emulsion having fine emulsified particles by high shearing force using, for example, a high-pressure homogenizer under high pressure. is.

When the (A) ultrafine emulsion of the present invention is used in an oil-in-water emulsified cosmetic, it is preferably 10 to 50% by mass in the cosmetic. (A) The ultrafine emulsion is a high-pressure emulsified part composed of a finely emulsified anionic surfactant, oil, and water.

(a1) Anionic Surfactant The anionic surfactant that can be used in the present invention is not particularly limited, but examples include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate (e.g., POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (e.g., sodium lauroyl sarcosinate, etc.) ; Higher fatty acid amide sulfonate (e.g., N-myristoyl-N-methyltaurate sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); Phosphate ester salt (POE-sodium oleyl ether phosphate, POE -stearyl ether phosphate, etc.); , sodium linadodecylbenzenesulfonate, triethanolamine linadodecylbenzenesulfonate, linadodecylbenzenesulfonic acid, etc.); higher fatty acid ester sulfate salt (e.g., hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); N-acylglutamate ( For example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (for example, funnel oil, etc.); POE-alkyl ether carboxylic acid; Ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate; higher fatty acid alkylolamide sulfate; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanol amines; sodium caseinate; etc.
Among these, long-chain acyl sulfonate type anionic surfactants, N-long-chain acyl acidic amino acid salts, soaps and the like are excellent.
More preferred are sodium stearoylmethyltaurate, sodium N-stearoyl-L-glutamate, sodium N-lauroyl-L-glutamate, potassium N-myristoyl-L-glutamate, stearic acid, lauric acid, behenic acid and the like.

As (a1) anionic surfactants, commercially available products include sodium stearoyl glutamate (Amisoft HS-11P (F) manufactured by Ajinomoto Co.), sodium lauroyl glutamate (Amisoft LS-11 manufactured by Ajinomoto Co.), potassium myristoyl glutamate (Amisoft MK-11, manufactured by Ajinomoto Co.), sodium myristoyl glutamate (Amisoft MS-11, manufactured by Ajinomoto Co.), and the like.

(a2) Linear higher alcohol having 16 or more carbon atoms (a2) The linear higher alcohol having 16 or more carbon atoms is not particularly limited as long as it can form α-gel in water together with (a1). Linear higher alcohols having 16 or more carbon atoms include laurin alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerene ether (bacyl alcohol), and 2-decyltetradecinol. , lanolin alcohol, cholesterol, hexyldodecanol, isostearyl alcohol, octyldodecanol and other linear and branched higher alcohols.

(B) stearoxyhydroxypropylmethylcellulose used in the present invention is represented by the following general formula (1).

In the above general formula (1), R ₁ , R ₂ and R ₃ are the same or different and are -[CH2CH(CH3)O]x- _R4 , -[ _CH2CH2O ]y _{- R4} , and --[CH ₂ CH(OH)CH ₂ O]z--R ₄ . Here, x, y and z are the same or different and represent integers from 0 to 4.
R ₄ represents one or more groups selected from a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear alkyl group having 10 to 28 carbon atoms. and at least one R ₄ in general formula (1) is a linear alkyl group having 10 to 28 carbon atoms. The linear alkyl group having 10 to 28 carbon atoms preferably includes a linear alkyl group having 12 to 22 carbon atoms.
In general formula (1), n represents an integer of 200-200,000.

(B) stearoxyhydroxypropyl methylcellulose is commercially available from Daido Kasei Co., Ltd. under the trade name of Sangelose, such as "Sangelose 90L", "Sangelose 90M", and "Sangelose 60L". is mentioned.

(B) stearoxyhydroxypropylmethylcellulose used in the present invention, when used in an oil-in-water emulsified cosmetic, can be blended in an amount of 0.2 to 2% by mass in the cosmetic, and 0.3 to 1%. Blending is more preferred.

(C) Nonionic Surfactants Examples of nonionic surfactants that can be used in the present invention include polyoxyethylene fatty acid glyceryl, polyoxyethylene/methylpolysiloxane copolymer, fatty acid polyoxyethylene sorbitan, and polyoxyethylene alkyl. Ethers, maltitol hydroxyaliphatic alkyl ethers, alkylated polysaccharides, alkyl glucosides, sucrose fatty acid esters, polyoxyethylene hydrogenated castor oil glyceryl, polyoxyethylene cetyl ether,
polyoxyethylene hydrogenated castor oil, polyoxyethylene glyceryl isostearate N,
Polyoxyethylene phytosterol, polyoxyethylene behenyl ether, polyoxyethylene sorbitan monostearate and the like.
Among these, those having an HLB of 8 or more are particularly preferable.

Commercially available nonionic surfactants (C) used in the present invention include Nikkor HCO-60 (manufactured by Nikko Chemicals Co., Ltd.), Elemax GWIS-160N (manufactured by Nihon Emulsion Co., Ltd.), Nikkor BPS-30 (Nikko Chemicals Co., Ltd.), Nikkol BB-20 (manufactured by Nikko Chemicals Co., Ltd.), Nikkol TS-10V (manufactured by Nikko Chemicals Co., Ltd.), sorbitan laurate ((NIKKOL (registered trademark) SL-10 and LM, Nikko Chemicals Co., Ltd.) (Emazol (registered trademark) 110, Kao Corporation)), sorbitan palmitate (NIKKOL (registered trademark) SP-10, Nikko Chemicals), sorbitan oleate (NIKKOL (registered trademark) SO-10V, Nikko Chemicals), Sorbitan stearate (NIKKOL (registered trademark) SS-10, Nikko Chemicals), sorbitan isostearate ((NIKKOL (registered trademark) SI-10PKV, Nikko Chemicals), sorbitan sesquioleate ((NIKKOL (registered trademark) SO- 15, Nikko Chemicals); (Rhedol (registered trademark) AO-15, Kao Corporation); (NOFABLE (registered trademark) SO-852S, NOF Corporation)), sorbitan trioleate ((Rhedol (registered trademark) SP- O-30, Kao Corporation); (NOFABLE (registered trademark) SO-853S, NOF Corporation)), sorbitan tristearate (NIKKOL (registered trademark) SS-30V, Nikko Chemicals), sorbitan sesquiisostearate (Estemol (registered trademark) 182V, Nisshin OilliO Group), polysorbate 60 ((Tween (registered trademark) 60, Croda International); (NIKKOL (registered trademark) TS-10V, Nikko Chemicals)), polysorbate 80 ((Rheodor (registered trademark) TWO-120, Kao Corporation; (NIKKOL (registered trademark) TO-10V, Nikko Chemicals)) and the like.
PEG-5 glyceryl stearate (EMALEX (registered trademark) GWIS GM-5, Nihon Emulsion Co., Ltd.), PEG-20 glyceryl stearate (POEM S-120, PEG-8 glyceryl isostearate (EMALEX (registered trademark) GWIS-108 , Nippon Emulsion Co.)), PEG-20 glyceryl isostearate (EMALEX (registered trademark) GWIS-120, Nippon Emulsion Co.), PEG-60 glyceryl isostearate (EMALEX (registered trademark) GWIS-160N, Nippon Emulsion Co.), isostearin PEG-90 glyceryl acid (EMALEX (registered trademark) GWIS-190, Nippon Emulsion Co., Ltd.), PEG-5 glyceryl triisostearate (EMALEX (registered trademark) GWIS-305, Nippon Emulsion Co., Ltd.), PEG-20 glyceryl triisostearate ( EMALEX (registered trademark) GWIS-320EX, Nippon Emulsion Co., Ltd.), PEG-20 glyceryl triisostearate (EMALEX (registered trademark) GWIS-320, Nippon Emulsion Co., Ltd.), PEG-20 hydrogenated castor oil isostearate (EMALEX (registered trademark) ) RWIS-120, Nihon Emulsion Co., Ltd.), PEG-5 glyceryl triisostearate (EMALEX (registered trademark) RWIS-305, Nihon Emulsion Co., Ltd.), glyceryl stearate (SE) (Sunsoft (registered trademark) 30 (Tenos), Taiyo Kagaku Co., Ltd.), glyceryl stearate (Sunsoft (registered trademark) 8004, Taiyo Kagaku Co., Ltd.); (NIKKOL (registered trademark) MGS-EEXV, Nikko Chemicals Co., Ltd.)), glyceryl oleate ((Sunsoft (registered trademark) 301V and O-30S, Taiyo Kagaku Co.), (Rheodor (registered trademark) MO-60, Kao Corporation)), cottonseed fatty acid glyceryl (Sunsoft (registered trademark) 8080, Taiyo Kagaku Co.), and the like.

The (C) nonionic surfactant used in the present invention is preferably 0.1 to 1% by mass in the cosmetic when used in an oil-in-water emulsified cosmetic. If it exceeds 1%, it may be unfavorable in that it tends to gel at high temperatures. On the other hand, if it is less than 0.1%, the viscosity required by the present invention cannot be obtained, and there is a tendency of separation, which is not preferable in some cases.

In the range of 1:0.3 to 1:4, the blending ratio of (C) nonionic surfactant to (B) stearoxyhydroxypropyl methylcellulose is in the range of 1:0.3 to 1:4, and the appearance is maintained in high viscosity water. It was found that an oil-type emulsified cosmetic was obtained. If it exceeds 1:4, it may be unfavorable in that the gelling tendency becomes strong. On the other hand, if the ratio is less than 1:0.3, it may be unfavorable in that it tends to separate due to a decrease in viscosity.

(A) ultrafine emulsion, (B) stearoxyhydroxypropyl methylcellulose, and (C) nonionic surfactant obtained by blending the oil-in-water emulsified cosmetic has a viscosity of
2,000 to 100,000 mPa·s is preferable, and 2,000 to 10,000 mPa·s is preferable in that it is gel-like when placed on the skin, but immediately changes to a liquid state by sharing to give a fresh feeling in use.

The oil-in-water emulsified cosmetic of the present invention is prepared by blending various components for making the cosmetic into the oil-in-water emulsified cosmetic. Various other components are blended into the aqueous phase (continuous phase) or oil phase (dispersed phase) of the oil-in-water emulsion according to their properties.

[Other components]
Cosmetics using the raw material for cosmetics according to the present invention may contain other ingredients, such as inorganic powders, organic powders, esters, anionic surfactants, cationic surfactants, as long as the effects of the present invention are not impaired. Amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film agents, UV absorbers, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, high Molecular emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant auxiliaries, fragrances, water, etc. can be blended as necessary, and the product can be produced by a conventional method according to the desired dosage form. I can.

Inorganic powders include, for example, talc, boron nitride, sericite, natural mica, calcined mica, synthetic mica, synthetic sericite, alumina, mica, kaolin, bentonite, smectite, calcium carbonate, magnesium carbonate, calcium phosphate, silicic anhydride, oxide Magnesium, tin oxide, iron oxide, yttrium oxide, chromium oxide, zinc oxide, cerium oxide, aluminum oxide, magnesium oxide, chromium hydroxide, Prussian blue, ultramarine blue, calcium phosphate, aluminum hydroxide, barium sulfate, magnesium sulfate, silicic acid, silica magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, aluminum silicate, strontium silicate, silicon carbide, magnesium fluoride, metal tungstate, magnesium aluminate, magnesium aluminometasilicate, chlorohydroxy aluminum, Clay, zeolite, hydroxyapatite, ceramic powder, spinel, mullite, cordierite, aluminum nitride, titanium nitride, silicon nitride, lanthanum, samarium, tantalum, terbium, europium, neodymium, Mn-Zn ferrite, Ni-Zn ferrite, silicone cover Eat, cobalt titanate, barium titanate, iron titanate, lithium cobalt titanate, cobalt aluminate, antimony-containing tin oxide, tin-containing indium oxide, magnetite, aluminum powder, gold powder, silver powder, platinum powder, copper powder, precious metal colloid, Iron powder, zinc powder, cobalt blue, cobalt violet, cobalt green, low order titanium oxide, fine particle titanium oxide, butterfly-like barium sulfate, petal-like zinc oxide, tetrapod-like zinc oxide, fine particle zinc oxide, titanium oxide as a pearl pigment Coated mica, titanium oxide-coated mica, titanium oxide-coated synthetic mica, titanium oxide-coated silica, titanium oxide-coated synthetic mica, titanium oxide-coated talc, zinc oxide-coated silica, titanium oxide-coated colored mica, red iron oxide-coated mica titanium, red iron oxide-black oxide Iron-coated mica titanium, carmine-coated mica titanium, konjo-coated mica titanium and the like can be mentioned.

Organic powders (e.g. silicone elastomer powder, silicone powder, silicone resin-coated silicone elastomer powder, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder (e.g. methyl methacrylate crosspolymer), polystyrene powder, styrene and acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); organic pigments such as zirconium, barium or aluminum lakes (e.g. organic pigments such as No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404;

Examples of anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate salts (e.g., POE -triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (e.g., sodium lauroyl sarcosinate, etc.); higher fatty acid amide sulfonates (e.g., sodium N-myristoyl-N-methyltaurate, coconut oil) fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); phosphate ester salts (POE-oleyl ether phosphate, POE-stearyl ether phosphate, etc.); , monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); etc.); higher fatty acid ester sulfate (e.g., hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); monosodium glutamate, etc.); sulfated oil (e.g., funnel oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; higher fatty acid alkylolamide sulfate; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; sodium caseinate and the like.

Cationic surfactants include, for example, alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts; Poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salts; alkyldimethylbenzylammonium salts; alkylisoquinolinium salts; dialkylmorphonium salts; POE-alkylamines; alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

Amphoteric surfactants include, for example, imidazoline-based amphoteric surfactants (e.g., 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (e.g., 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amidobetaine , sulfobetaine, etc.) and the like.

Lipophilic nonionic surfactants include, for example, sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.); hydrogenated castor oil derivatives; glycerin alkyl ether, etc. be done.

Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.). ;POE-sorbitol fatty acid esters (eg, POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerin fatty acid esters (eg, POE - POE-monooleate, such as glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.); POE-fatty acid esters (e.g., POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.) ); POE-alkyl ethers (e.g., POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic types ( POE POP-alkyl ethers (e.g., POE POP-cetyl ether, POE POP-2-decyltetradecyl ether, POE POP-monobutyl ether, POE POP-hydrogenated lanolin, POE POP-glycerin ether, etc.); tetra-POE, tetra-POP-ethylenediamine condensates (e.g., Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE- hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic monoisostearate diester, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax lanolin derivatives (for example, POE-Sorbit beeswax, etc.); alkanolamides (e.g., coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; ester; alkylethoxydimethylamine oxide; trioleyl phosphate and the like.

Examples of moisturizing agents include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caroninic acid, atelocollagen, and cholesteryl-12-hydroxystearate. , sodium lactate, bile salts, dl-pyrrolidone carboxylate, alkylene oxide derivatives, short-chain soluble collagen, diglycerin (EO) PO adducts, rose barra extract, yarrow extract, melilot extract and the like.

Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algecolloid (cassou extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial macromolecules (e.g., xanthan gum, dextran, succinoglucan, bullulan, etc.); animal macromolecules (e.g., collagen, casein, albumin, gelatin, etc.), etc. is mentioned.

Examples of semi-synthetic water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, , hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.); alginate-based polymers (eg, sodium alginate, propylene glycol alginate, etc.);

Examples of synthetic water-soluble polymers include vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer, etc.); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40 acrylic polymers (eg, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers, and the like.

Thickeners include, for example, gum arabic, carrageenan, karaya gum, tragacanth gum, carob gum, quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium araginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, A1 Mg silicate (Vegum), Examples include laponite and silicic anhydride.

Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (e.g., para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester. , N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); Salicylic acid-based UV absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (e.g., octyl methoxycinnamate, ethyl -4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxy Cinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl -α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone-based UV absorbers (e.g., 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl- benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3-(4′-methylbenzylidene)-d,l-camphor, 3 -benzylidene-d,l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2-(2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2-(2′-hydroxy-5′-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4′-t-butyldibenzoylmethane; 5-(3,3-dimethyl-2- norbornylidene)-3-pentan-2-one, dimorpholinopyridazino; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 2,4-bis-{[4-(2-ethylhexyloxy)-2 -hydroxy]-phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine and the like.

Examples of sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. , sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate, and the like.

Examples of lower alcohols include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Polyhydric alcohols include, for example, dihydric alcohols (e.g., ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.); tetrahydric alcohols (e.g., 1,2,6 -pentaerythritol such as hexanetriol); pentahydric alcohols (e.g., xylitol, etc.); hexahydric alcohols (e.g., sorbitol, mannitol, etc.); polyhydric alcohol polymers (e.g., diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); dihydric alcohol alkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc. ); dihydric alcohol alkyl ethers (e.g., diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dihydric alcohol ether ester (e.g., ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazibate, ethylene glycol disuccinate); diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ethers (e.g., xyl alcohol, selachyl alcohol, batyl alcohol, etc.); sugar alcohols (e.g., sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitose, starch-degrading sugar reducing alcohol, etc.) ); Glysolid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-Butyl ether; POP-POE-Butyl ether; Tripolyoxypropylene glycerin ether; -Pentaneerythritol ether, polyglycerin, and the like.

Monosaccharides include, for example, 3-carbon sugar (eg, D-glycerylaldehyde, dihydroxyacetone, etc.); 4-carbon sugar (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.); 5-carbon sugar (eg, , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc.); hexoses (e.g., D-glucose, D-talose, D -Busicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); seven-carbon sugar (e.g., aldoheptose, heprose, etc.); eight-carbon sugar (e.g., octulose, etc.); deoxy sugar ( For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.); Amino sugars (for example, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.) ); uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.), and the like.

Oligosaccharides include, for example, sucrose, guntianose, umbelliferose, lactose, planteose, isolignoses, α,α-trehalose, raffinose, lignoses, umbilicine, stachyose, verbascoses and the like.

Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, and keratosulfate. , locust bean gum, succinoglucan, caroninic acid and the like.

Amino acids include, for example, neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl β-alanine, glutathione, pyrrolidone carboxylic acid and the like.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. is mentioned.
Examples of polymer emulsions include acrylic resin emulsions, polyethyl acrylate emulsions, acrylic resin liquids, polyacryl alkyl ester emulsions, polyvinyl acetate resin emulsions, and natural rubber latex.

Examples of pH adjusters include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
Examples of antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.

Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

Other ingredients that can be blended include, for example, preservatives (ethylparaben, butylparaben, chlorphenesin, phenoxyethanol, etc.); ); whitening agent (e.g., placenta extract, saxifrage extract, arbutin, etc.); , coix seed, loofah, lily, saffron, cnidium, ginger, hypericum, ononis, garlic, hot pepper, chimp, angelica, seaweed, etc.), activator (e.g., royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (e.g., , Nonylic Acid Valenylamide, Nicotinic Acid Benzyl Ester, Nicotinic Acid β-Butoxyethyl Ester, Capsaicin, Zingerone, Cantharis Tincture, Ictamol, Tannic Acid, α-Borneol, Tocopherol Nicotinate, Inositol Hexanicotinate, Cyclanderate, Cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthine, γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.), and the like.

Furthermore, sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, malic acid, caffeine, tannin, verapamil, tranexamic acid and its derivatives, licorice, Various crude drug extracts such as Chinese quince and Ichiyakko, medicines such as tocopherol acetate, glycyrrhizic acid, glycyrrhizic acid and its derivatives or salts thereof, whitening agents such as vitamin C, magnesium ascorbate phosphate, ascorbate glucoside, arbutin, kojic acid, etc. Amino acids such as arginine and lysine and derivatives thereof, sugars such as fructose, mannose, erythritol, trehalose and xylitol may also be added as appropriate.

The product form of the oil-in-water emulsified cosmetic according to the present invention can take any product form. Specifically, product forms include skin care cosmetics such as moisturizing gels, massage gels, serums, lotions, milky lotions, makeup cosmetics, sun care products, hair cosmetics such as hair setting agents and hair gels, and hair dyes. can take

[Method for producing oil-in-water emulsified cosmetic according to the present invention]
It can be manufactured by a known method. For example, dissolving stearoxyhydroxypropyl methylcellulose and a nonionic active agent in water (A). A portion of water, oil, and an anionic active agent are emulsified under high pressure to prepare an ultrafine emulsion (B).
By mixing (A) and (B), it is possible to produce an oil-in-water emulsified cosmetic with an appropriate viscosity range.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto. Unless otherwise specified, the blending amount is shown in % by mass relative to the system in which the component is blended.
Before describing the examples, the method for evaluating the oil-in-water emulsified cosmetic according to the present invention will be described.

Evaluation (1): Evaluation of Transparency Transparency is judged by L-value measurement and final appearance on ultrafine emulsion parts. Ultrafine emulsion parts are measured with a NIPPON DENSHOKU Spectrophotometer SE700, and the L value is confirmed to be between 30 and 90. In addition, the appearance is judged by putting it in a 50g glass container and checking whether the scenery behind it can be seen through.

○ Back view is transparent
× The scenery behind is not transparent

Evaluation (2): Evaluation of Viscosity Viscosity (mPa·s/30° C.) is measured by DIGITAL VISMETRON VDA manufactured by SHIBAURA SYSTEMS CO., LTD.
The measurement conditions are to use rotor No. 3 or 4 and set the numbers at 12 rpm/1 minute.
Viscosity measurement
A rating 2000 to less than 10,000 mPa・s
B evaluation Less than 2000mPa・s or more than 10,000mPa・s
C rating not measurable

First, the present inventors produced an ultrafine emulsion used in the present invention, using a general thickener, (C) a nonionic surfactant, and (A) an average emulsion particle size of 5 nm to 300 nm We investigated whether ultrafine emulsions can be thickened.

(*1) Olefin Oligomer 30 (manufactured by Nisshin OilliO Co., Ltd.)
(*2) Aristflex HMB (manufactured by Clariant Japan Co., Ltd.)
(*3) Sangelose 90L (manufactured by Daido Kasei Kogyo Co., Ltd.)
(*4) Emalex 125 (Nippon Emulsion Co., Ltd.)

From these results, it was found that a combination of a general thickener and a nonionic surfactant could not give the ultrafine emulsion a sufficient viscosity, resulting in a poor appearance.
On the other hand, it was found that a combination of (B) stearoxyhydroxypropyl methylcellulose and (C) a nonionic surfactant can increase the viscosity while maintaining the appearance.

Next, the present inventors examined the blending amount of (B) stearoxyhydroxypropylmethylcellulose.

From these results, it was found that when the content of (B) stearoxyhydroxypropylmethylcellulose is in the range of 0.2% by mass or more, an oil-in-water emulsified cosmetic having a high viscosity while maintaining a good appearance can be obtained.

Next, the present inventors examined the compounding amount of (C) the nonionic surfactant.

From these results, the external appearance was maintained well when the compounding ratio of (C) nonionic surfactant to (B) stearoxyhydroxypropyl methylcellulose was in the range of 1:0.3 to 1:4. It was found that an oil-in-water emulsified cosmetic having a high viscosity can be obtained.

Next, the present inventors examined the types of (C) nonionic surfactants.

(*5) Nikkor HCO-60 (manufactured by Nikko Chemicals Co., Ltd.)
(*6) Emarex GWIS-160N (manufactured by Nippon Emulsion Co., Ltd.)
(*7) Nikkor BPS-30 (manufactured by Nikko Chemicals Co., Ltd.)
(*8) Nikkor BB-20 (manufactured by Nikko Chemicals Co., Ltd.)
(*9) Nikkor TS-10V (manufactured by Nikko Chemicals Co., Ltd.)

From these test examples, it was found that (C) a variety of nonionic surfactants increase the viscosity. In particular, the hydrophilic nonionic activator produced a product having favorable appearance and viscosity.

The present inventors further describe formulation examples of the oil-in-water emulsified cosmetic according to the present invention below.

Claims (2)

(A) 10 to 50% by mass of an ultrafine emulsion containing the following (a1) to (a4) ;
(a1) sodium stearoyl glutamate
(a2) stearyl alcohol and behenyl alcohol
(a3) Oil droplets with an average particle diameter of 5 nm to 300 nm
(a4) water
(B) 0.2 to 2% by mass of stearoxyhydroxypropyl methylcellulose represented by the following general formula (1);
(C) 0.1 to 1% by mass of a nonionic surfactant;
including
The blending ratio of (B) and (C) is 1:0.3 to 1:4
An oil-in-water emulsified cosmetic characterized by:

In general formula (1), R1, R2, and R3 are the same or different, and one or more selected from -[CH2CH(CH3)O]x-R4 and -[CH2CH(OH)CH2O]z-R4 indicates a group. Here, x, y and z are the same or different and represent integers from 0 to 4.
R4 represents one or more groups selected from a hydrogen atom, a linear or branched alkyl group having 1 carbon atom, and a linear alkyl group having 18 carbon atoms, and is represented by the general formula ( In 1), at least one R4 is a linear alkyl group having 18 carbon atoms.
In general formula (1), n represents an integer of 200-200,000. 2. The oil-in-water emulsified cosmetic according to claim 1, wherein the viscosity is from 2000 to 100000 mPa·s.